Carbon remover and metal surface cleaning composition



Patentcd May 30, 1950 UNITED STATES 2,509,197 CARBON REMOVED AND METAL SURFACE CLEANING COMPOS ON Ben Borns, Hartsdale, N. Y., and George Ambrose Martin, East Alton, 111., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application January 16, 1948,

Serial No. 2,814

8 Claims. (Cl. 252-118) This invention relates to the removal of undesirable foreign deposits from the metal surfaces. More particularly this invention pertains to the removal of hard carbonaceous materials, resins, varnish, lacquers, rust, abrasives, welded metal particles, and the like, from engines, turbines, industrial equipment and the like by applying thereto a novel chemical composition, each component thereof being within rather specific proportions, said composition having the ability of penetrating through the deposits, loosening it and facilitating in removing it from the metal surface, leaving the engine or other metal surfaces clean and undamaged.

The development of high power engines operating at relatively very high temperatures and heavy loads, such as internal combustion engines. Diesel engines, gasoline aircraft engines, jet engines, form, during their operation, carbon and sludge deposits which cause sticking, clogging, and wear of movable parts. This results in wear and corrosiomof engine parts, and generally reduces the operating eilicienoy of the engine. Present developments in gas turbine engines which operate at such elevated temperatures as from 1100 F. to 1800 F. greatly accentuate this problem. Thus, gas turbine engine parts such as the compressor blades, and turbo-jet units such as turbo-supercharged engines, as well as other industrial units such as heat exchange elements, torque converter transmissions, air and gas compressor valves, etc., become coated within relatively short periods of time with thick layers of carbonaceous and other foreign deposits which must be removed. These deposits adhere so tenaciously to the surface that the only way to remove them at present is by hand scraping or by soaking in chemical solutions for long periods of time. Such drastic treatment usually results in damage caused by corrosion or pitting of the treated metal surface due to the chemical nature of the material used to remove the deposits,

, swelling or destruction of insulating and nonmetallic parts, and chipping or cracking of metal surfaces due to hand scrubbing and cleaning. In addition present known deposit removers are highly toxic due to their high content of phenolic and/or halogen-containing materials which are a hazard and are detrimental to the health of the user. Known deposit removers also introduce a fire hazard problem due to the fact that such materials have low flash points but are only efiective at elevated temperatures.

It is an object of this invention to provide a cleaning and deposit-removing composition which can be easily and readily applied to heav- I 2 corrosive to the metal being cleaned and which is non-reactive with non-metallic parts with which it might come in contact. Still another object of this invention is to provide a cleaning composition which is safe to use within'a relatively wide temperature range.

The above and other objects may be attained in accordance with the present invention by admixing, with a suitable hydrocarbon base, certain chemically active ingredients in rather specific proportions, each of which exerts a specific function and a co-ordinating one with the composition taken as a whole which results in a potent cleaning composition. The active ingredients of this invention comprise a hydrocarbon base admixed with specific types of detergent, wetting and coupling agents, a penetrant and water, all of which are essential. A criteria. of compositions of this invention is that all ingredients which comprise it must be present at all times and in relatively specific proportional relationship to each other.

The base comprises essentially a hydrocarbon having a boiling point above that of room temperature and up to the boiling temperatures of mineral lubricating oil fractions. The selection of the type of hydrocarbon base to be used depends primarily upon the intended use of the composition. Thus, if the composition is to be used mainly as a carbon remover, a relatively light petroleum hydrocarbon fraction, such as kerosene, is preferred, although mineral seal oil, gas oil, various petroleum naphtha cuts, mineral spirits, kerosene S02 extracts, aromatic solvents, petroleum ether, aromatic hydrocarbons such as benzene, p-xylene, o-xylene, m-xylene, cumene, butylbenzenes parafiinic hydrocarbons, e. g. normal hexane, dimethyl pentane, octane, iso-octane, undecane, dodecane; cycloparaffins, e. g. cyclohexane, methylcyclohexane, isopropylcyclohexane, can be 'used. In cases where compositions of this invention are to be used as flushing oils in addition to functioning as carbon and engine deposit removers, a petroleum hydrocarbon having some lubricating properties such as a mineral lubricating oil should be used. The amount of base used can vary from between about 12% to about by weight, and preferably between about 12% and 20% by' weight of the composition.

Detergents of this invention function both in a chemical and physical manner. Primarily they help to keep. finely divided carbon and resinous particles formed during operation of internal combustion engines, turbines and the like or deposits already formed but loosened from a surface by suitable means, in a state of suspension thereby preventing their adherence to or build-up on a surface. This is due to the adsorptive action of the detergents, making the carbon particles and other deleterious matter with which they come in contact large enough and light enough so that their settling rate is greatly retarded and therefore they tend to remain in suspension. In addition the detergents co-act with other constituent materials of this invention so as to aid in loosening and removing deposits from surfaces and at the same time not interfere with the activity of other additives present. They are also relatively thermally stable and resist oxidation.

It has been found that particularly suitable detergents which have the above properties when employed in conjunction with other additives of this invention are non-hydroxy containing polyamine salts of organic and inorganic acids. The polyamines which can be used to form the detergent salts of this invention are the aliphatic polyamines which can contain substituent nonhydroxy groups such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, tetramethyl methylenediamine,

. propylene diamine, dipropylene triamine, N.N-

. amine, N-n-tetradecyl diethylene triamine. N-nhexadecyl triethylene tetramine, N-octyl ethylene diamine, N-2 ethyl hexyl N-hexadecyl triethylene tetramine,N'-hepty1 trimethylene diamine, N-tetradecyl tripropylene tetramine, 1.3 diamino propane, 3 diethyl amino propylamine, 1.3 diamino butane, 1,3 bis ethyl amino butane, 1.10 decylene diamine. phenyl ethylene diamine, di-o-tolyl ethylene diamine, and the like. Mixtures of such compounds consisting either of compounds derived from the same alkylene polyamine with different alkyl substituents. such as would result on treating ethylene diamine with mixed alkyl chlorides, or mixtures of varying degrees of alkylation or mixtures containing compounds derived from different alkylene polyamines with the same or different or mixed alkyl substituents are also contemplated for use herein.

Acids which can be used to combine with the above-mentioned polyamines to form detergent salts may include:

I. Aliphatic acids. e. g. capric, undecanoic, lauric, myristic, palmitic, stearic. arachidic, sorbic, oleic, ricinoleic, linoleic, linolenic. elaidic. erucic, brassidic, clupanodonic, mono. di and tri hydroxy-stearic. 'alkyl malonic. alkyl succinic, alkyl glutaric. alkyl maleic. alkyl malic, alkyl tartaric, alkyl citric, alkvl adipic. tartronic acids and the like. Also synthetic acids prepared by oxidizing hydrocarbons such as parailinic wax can be used as well as fatty oils containing substantial amounts of free fatty acids. Among the fatty oils which can be used for this purpose are: olive oil, castor oil, peanut oil. rapeseed oil, cottonseed oil. sesame oil and the like.

II. Aromatic acids: Benzoic, salicylic, cinnamic. hydrocinnamic. phthalic, naphthoic, abietic, resinic. phenyl acetic to phenyl stearic, resorcylic, gallic, toluic, xylic, lauroxy and phenoxy benzoic acids and the like.

III. Cyclic acids: Naphthenic acids derived from petroleum hydrocarbons, cyclohexane carboxylic, tetrahydrophthalic, tetrahydrotoluic, camphane-3-carboxylic, cholic, cyclohexylacetic, cyclohexylbutyric, cyclohexylcaproic, cyclohexylvaleric acids and the like.

IV. Heterocyclic acids: Picolinic, nicotinic, isonicotinic, quinolinic, chinchomeronic, lutidinic,

4 boxylic, furan carboxyllc. Dyrrol carboxylic acids and the like.

V. Organic compounds containing inorganic acids: (A) Benzene sulionic acid, toluene sulfonic acid, triisopropyl naphthalene sulfonic acid, diphenyl sulfonic acid, polyamyl naphthalene sulfonic acid, diwax benzene sulfonic acid, xylene sulfonic acid, benzene disulfonic acid, wax sulfo succinic acid, diwax naphthalene sulfonic acid, petroleum sulfonic acids derived from various petroleum fractions such as: gas oil, kerosene, light oil, turbine oil, mineral lubricating oil, petroleum waxes, petrolatum, etc.; (13) Phosphorus-containing acids, such as obtained by reacting P285, P205, P483, and the like with oletlnic hydrocarbons, aromatic hydrocarbons, phenolic compounds, alcohols, organic acids as listed above and mixtures thereof and the like.

The oxygen atoms in the carboxyl radical of the acids under groups I to IV may be replaced by S, Se, and/or Te atoms resulting in the following acid radicals: CSOH, COXH, CXXH, where X is S, Se or Te. Also any of the above acids may contain non-polar and/or polar substituent groups such as: alkyl, mercapto, hydroxy, amino, cyano, isocyano, nitroso, nitro, alkoxy aroxyl and the like.

Specific polyamine salts which are preferred for use in compositions of this invention are:

Ethylene diamine oleate Diethylene triamine oleate Propylene diamine oleate Dipropylene triamine oleate .Ethylene diamine stearate Ethylene diamine palmitate Ethylene diamine ricinoleate Diethylene triamine stearate Diethylene triamine palmitate Diethylene triamine ricinoleate Ethylene diamine hydroxy stearate Ethylene diamine petroleum sulfonate Propylene diamine petroleum sulfonate Ethylene diamine trioctyl phosphate Tripropylene tetramine oleate N-n-dodecyl diethylene triamine oleate N-n-dodecyl diethylene triamine ricinoleate N-octyl ethylene diamine oleate N-octyl ethylene diamine petroleum sulfonate N-octyl ethylene diamine ricinoleate N-octyl ethylene diamine caprylate N-octyl ethylene diamine laurate Ethylene diamine diisopropyl salicylate Ethylene diamine dioctyl benzoate Ethylene diamine naphthenate Ethylene diamine phenyl stearate Propylene diamine diisopropyl salicylate Propylene diamine naphthenate Ethylene diamine diwax naphthalene sulfonate,

etc.

The amount of polyamine salt detergent which can be used in compositions of this invention may vary from about 2 to 15% and preferably is kept within range of between 4% to 8% by weight.

The function of good penetrant is to penetrate through interfering layers of deleterious materials and loosen them from the surface to which they adhere. To accomplish this a penetrant must possess low degree of volatility, low surface tension and high capillary or creeping properties so that once having penetrated through the foul matter adhering to a surface it can displace it therefrom and leave on said surface a protective oiliness film which if desired can be easily removed by flushing, for example, with steam and cynchomeronic, pyrole carboxylic, thiophene car- 18 the like. The protective film acts as a boundary a separator between contacting surfaces thereby protecting them from wear and the like. Penetrants which are particularly suitable due to their co-ordinate action with other constituents of this 6 coupling agents are polyhydric organic deriva-- tives such as alkylene glycols; diglycols, e. g. dipropylene glycol, dibutylene glycol, diamyiene glycol; triglycol, e. g. tripropylene glycol; ether invention so as to produce a product having max- 5 alcohols containing up to 20 carbon atoms and imum efliciency in removing foul matter from more particularly glycol mono-alkyl ethers, e. g. surfaces are halogenated aliphatic and aromatic the cellosolves, e. g. ethylene glycol mono-ethyl 7 compounds, e. g. trichloroethylene, 2,2-dichloro ether, ethylene glycol mono-p'ropyl ether, ethylene ethylether, o-dichlorobenzene, dichloroisopropylglycol mono-n-butyl ether, ethylene glycol monoether, etc; ketones, e. g. mesityl oxide, isopho- In isobutyl ether, ethylene glycol mono-tert.butyl rone: and mixture of the above halogenated comether, ethylene glycol mono-hexyl ether, propylpounds and ketones. The penetrant generally ene glycol mono-ethyl ether, propylene glycol comprises approximately 20% to 50% by weight mono-isobutyl ether, etc.; diglycol mono-alkyl of the composition. ethers such as the carbitols, e. g. diethylene To activate and improve the general properties glycol mono-methyl ethyl normal and isopropyl of compositions under consideration a wetting ethers, diethylene glycol mono-butyl ether, diethagent is employed which co-acts with the above ylene glycol mono-decyl ether, etc.; also dipropylpenetrants and wets the surface which has been ene glycol mono-isopropyl ether, dipropylene glye rendered free of the deleterious materials by the col mono-ethyl ether, dipropylene glycol mono active ingredients of this composition. The sur- 2o isoamyl ether, dipropylene glycol mono-heptyl face thus wetted is protected and foul matter is ether, diisobutylene glycol mono-isopropyl ether, prevented from re-adhering to the cleaned surethylene-propylene glycol mono-ethyl ether, ethface. Wetting agents which are suitable for this ylene-isobutylene glycol mono-isopropyl ether, purpose are the polyamines referred to previously etc.; also, glycerine mono or di-ethers of 6 or more and alicyclic alcohols, etc. These types of com- 5 carbon atoms such as glycerine monoor dipropounds can best be illustrated by such specific pyl, butyl, amyl, etc. ethers; mono-esters of glycompounds as ethylene diamine, diethylene tricol or glycerine, etc. The amount of coupling amine, propylene diamine, dipropylenetriamine, agent used generally does not exceed 20% andis cyclohexanol, trimethyl-cyclohexanol and the preferably kept in the range of m like. The amines are particularly preferred, for The above classes of additives which constitute in addition to acting as wetting agents, they react the essential component parts of compositions of with acidic materials thereby continuously rethis invention have not been selected at random plenishing the detergent agent. The amount of but have been selected after careful and painstakwetting agent used ranges between about 2% and ing research and because of their coordinating about 25% and preferably is kept within 8% to action in aiding to remove deleterious engine 20% by weight of the total composition. deposits as well as removal of undesirable foreign Water is an essential component of the present deposits from various surfaces in general. composition. The exact function or mechanism To more fully illustrate the present invention of it is not understood, but in cases where water the following are a few compositions which have was eliminated as a component of the present to been compounded, tested and found extremely composition the eiliciency of the latter as a eflicient for removing deposits from metal surdeposit remover was reduced to such a degree faces and the like.

Composition, parts by wei ht Hydrocarbon Detergent Penetrant Wetting Agent Coupling Agent Water 1 Kerosene, 20. Ethylene diamine odichloro benaene,40--- ethlenediamine, 5.6 ethyleneglycolmonobutyl l5 oleate, 1. ether, 15. 2 D do do.....------.-.. ethylenediamine, 2.6 -.do l8 3 Do..----- pro pyleue diamine o.-.- propyienediamine, 2.5-- do 18 o eate, 4.5.

as to render it almost useless. t is noted t a so To test the effectiveness of compositions of this the wetting power of the composition is increased and the foreign matter is kept in a more permanent dispersion due to the presence of water. It therefore appears that water exerts a synergistic eflect and also acts as a carrier for foreign deposits loosenedfrom a surface. The amount of water used varies from between about 10% to about 20%, and preferably is-kept between about 12% and 15% by weight.

invention as removers of carbon and other deleterious materials from various surfaces the following tests were performed and results compared with the best known commercial materials used for the same purpose and with compositions similar to these of the present invention except that for polyamine salts, aliphatic mono amine and alkylolamine salts were used. Such compositions comprised for example the following con- In order to stabilize compositions under constituents:

- Commsitiompartsbyweiqht Hydrocarbon Detergent Tenetrant Wetting Agent Coupling Agent Water 4 Kerosene, 12. D i e t by 1 ethanol o-dichloro benzene, 40.-- diethylethanol amine, ethylene glycol monobutyl 12 amino oleate, 5.6. 20.4. ether, l0. l5 Kerosene, l9. Isopro'gaiiia: amine o-dichloro benzene, 47.-- digtliylethanol amine, ethtygene glycolmonohutyl 14 0 ea e er, 6 Kerosene, l2- lauryl a'mine naph' o-dichloro benzene, 40." diethylethanol amine, ethylene glycol monobutyl 12 thenate, 6.4. 19.6. ether. 10.

sideration so as to prevent separation and break down; a coupling agent is added. The preferable Example I.Steel panels were sprayed with a solution of oil sludge in carbon tetrachloride and initial deposit removal as well at time of complete removal were noted at a little above room tem- 8. A cleaning composition comprising a mixture of about 12% to about 50% by weight of kerosene. about 2% to about 15% by weight of ethylene diamine oleate, about 20% to about 40% by weight of c-dichlorobenzene, about 2% to about 25% by weight ofethylene diamine, about 10% to about 20% by weight of ethylene glycol monobutyl ether, and about 10% to about 20% by weight of water.

4. A cleaning composition comprising a mixture perature such as about 90 1". of from about 12% to about 50% by weight kero- Test Time of Initial Time at Com lets comma Temp. Removal, min. men.

'1'. Commercial Product 90 None after i!) Min..." Nous aftu m Mira--- No eflect, panel still heavily Composition 01am moms 2110 min Absolutely clean. Compodtion oi Ex. 2 00 0:50 min 0:10 min Do. Composition of Ex. 3.- 90 lzill min 8:10 min Do. Composition oi Ex. 4. 00 2:00 min 24:00 min Clean. Com tion oi x. 5 90 8:45 min 10:10 min. Do. Composition of Ex. 6 90 Ineflective at 90 F. Composition oi Ex. 5 185 417% at 10:00 min. Substantial deposit left.

Compositions of this invention are excellent deposit removers such as are termed on pancake valves of catalytic hydrocarbon compressors where it is not uncommon to find hard carbon deposits of over one-half inch in thickness on said valves and other parts of such equipment such as the cylinder walls, pistons, bearings and the like.

In addition compositions of this invention are excellent removers for deposits which are formed during operation of gas turbine engines. They also eiiectively remove scales, rust and corrosion deposits from metal surfaces such as boiler tubes, evaporation pipes, machines and the like. They are excellent degreasing compositions and are efiective dirt removers as well as paint and varnish removers. In addition to removing undesired deposits from metal surfaces they are equally effective for removing deposits from non-metallic surfaces.

Compositions of this invention are non-corrosive to metals. non-toxic and are not fire hazard. They have no harmful eflect when in contact with the skin, rubber, plastic surfaces and the like, and can be applied by any knownmeans such as spraying, immersing, dipping. swabbing and the like.

Itis to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however. is not to be limited thereto or otherwise restricted, except by the prior are and the scope of the appended claims.

We claim as our invention:

1. A cleanin composition comprising a mixture Per cent by weight Kerosene 20.0 Ethylenediamine oleate 4.4 o-Dichlorobenzene 40.0

Ethylene glycol mono butyl ether 15.0 Ethylene diamine 5.6 Water I 15.0

2. A cleaning compositon comprising a mixture sene, irom about 2% to about by weight of ethylene diamine oleate, from about to about 40% by weight of a chlorinated organic compound of the class consisting of o-dichlorobenzene, trichloroethylene, diohloroethyl ether and dichlor isopropyl ether, from about 2% to about by weight of ethylene diamine, from about 10% to about 20% by weight of ethylene glycol monobutyi ether and from about 10% to about 20% by weight water.

5. A cleaning composition comprising a mixture of from about 12% to about 50% by weight of kerosene, of from about 2% to about 15% by weight of ethylene diamine oleate, from about 20% to about by weight of o-dlchlorobenzene, from about 2% to about 25% by weight of propylene diamine, from about 10% to about 20% by weight of ethylene glycol monobutyl ether, and from about 10% to about 20% by weight of water.

6. A cleaning composition comprising a mixture of from about 12% to about by weight kerosene, from about 2% to about 15% by weight oi a lower aliphatic diamine salt of a high molecular weight fatty acid having 10 to 18 carbon atoms and wherein the diamine is selected from the group consisting ofethylene diamine and propylene diamine, from about 20% to about 40 96 by weight of a chlorinated organic compound selected from the class consisting of o-dichlorobenzene, trichlcroethylene, dichloroethyl ether and dichloroisopropyl ether, from about 2% to about 25% by weight of a lower aliphatic diamine selected from the group consisting of ethylene diamine and propylene diamine, from about 10% to about 20% by weight of an unsubstituted lower alkylene glycol monoalkyl ether of up to 20 carbon atoms and wherein the alkylene glycol is selected from the group consisting of ethylene glycol and propylene glycol and from about 10% to about 20% by weight water.

'7. Acleaning composition comprising a mixture of about 12% to about 50% by weight of kerosene, about 2% to about 15% by weight of an organic amine soap selected from the class consisting of ethylene diamine oleate and propylene diamine oleate, from about 20% to about 40% by weight of o-dichlorobenzene', from about 2% to about 25% by weight of a lower aliphatic diamine selected from the class consisting of ethylene diamine and propylene diamlne, from about 18.0 is 10% to about 20% by weight of ethylene glycol monobutyl ether, and from about 10% to 20% by weight of water.

8. A cleaning composition comprising a mixture of about 12% to about 50% by weight of a light liquid petroleum hydrocarbon solvent, about 2% to 15% by weight of an organic amine soap selected from the class consisting of ethylene diamine soap of a higher fatty acid having 10 to 18 carbon atoms and propylene diamine soap of a higher fatty acid having 10 to 18 carbon atoms, from about 20% to about 40% by weight of o-dichlorobenzene, from about 2% to about 25% by weight of a lower aliphatic diamine selected from the class consisting of ethylene diamine and propylene diamine, from about 10% to about 20% by weight of ethylene glycol monobutyl ether, and from about 10% to 20% by weight of water. BEN BORUB. GEORGE AMBROSE MARTIN.

7 10 REFERENCES CITED The following references are of record in the file of this patent! UNITED STATES PATENTS Borus Apr. 5, 1949 OTHER REFERENCES Ind. and Eng. Chem, vol. 27, No. 8 (Aug. 1935),

pages 867-871. 

7. A CLEANING COMPOSITION COMPRISING A MIXTURE OF ABOUT 12% TO ABOUT 50% BY WEIGHT OF KEROSENE, ABOUT 2% TO ABOUT 15% BY WEIGHT OF AN ORGANIC AMINE SOAP SELECTED FROM THE CLASS CONSTITUTING OF ETHYENE DIAMINE OLEATE AND PROPYLENE DIAMINE OLEATE, FROM ABOUT 20% TO ABOUT 40% BY WEIGHTG OF O-DICHLOROBENZE, FROM ABOUT 2% TO ABOUT 25% BY WEIGHT OF A LOWER ALIPHATIC DIAMINE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE DIAMINE AND PROPYLENE DIAMINE, FROM ABOUT 10% TO ABOUT 20% BY WEIGHT OF ETHYLENE GLYCOL MONOBUTYL ETHER, AND FROM ABOUT 10% TO 20% BY WEIGHT OF WATER. 